Open spaces and molecular motions of polyether-based network polymers probed by positron annihilation

The lifetimes of positrons have been measured for network polymers based on polyethers. From the temperature dependence of the lifetime of ortho-positronium (o-Ps), τ₃, for the network polymer of poly(ethylene oxide-co-propylene oxide) P(EO/PO)], an onset temperature for limited local motions of molecules, T_γ, and the glass transition temperature, T_g, were determined to be 57 and 201 K, respectively. For the network polymer of polyEO-co-2-(2-methoxyethoxy)ethyl glycidyl ether] P(EO/MEEGE)], T_γ and T_g were determined to be 57 and 185 K, respectively. For both specimens, above 270 K, the observed linear temperature dependence of τ₃ was attributed to the thermal expansion of open spaces in a liquid state. In the temperature range between T_γ and 270 K, for the P(EO/MEEGE) network, τ₃ was longer and its intensity was smaller than those for the P(EO/PO) network. These results were attributed to the increase in the size of open spaces for the P(EO/MEEGE) network polymer and the blocking of these regions by motions of side chains and chain ends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1919–1925, 1998